JPH05194479A - Derivative of 4-substituted 2,2-dihalogenobenzo(1,3)- dioxoles - Google Patents

Abstract

PURPOSE: To prepare the subject new compd. useful as raw materials for producing high activity pesticides or the like, such as anilne-benze[1,3]dioxoles.

CONSTITUTION: The compd. of formula I (R is fluorine, chorine, bromine or nitro; Hal is chlorine or fluorine), such as 4-bromo-2,2-difluoro-benzo[1,3]dioxole, can be obtd. by chlorinating the compd. of formula II, e.g. in the case Hal denotes chlorine. Moreover, it is obtd. by reacting the compd. of formula III with hydrogen fluoride in a solvent such as toluene in the case Hal denotes fluorine.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to 2,2 in which the 4-position is substituted.
-Dihalogenobenzo [1,3] dioxole novel derivatives, process for their preparation and highly active biocides such as anilino-benzo [1,3] dioxole
their use as starting materials for the production of des).

[0002]

2. Description of the Prior Art 4-Carboxy-benzo [1,3] dioxole is reacted with phosphorus pentachloride to give 2,2-dichloro-
Benzo [1,3] dioxolo-4-carbonyl chloride was converted to a 2,2-difluoro-4-carbonylfluoride derivative using antimony trifluoride and then a 4-carbamide derivative was obtained using ammonia. , And then converted to a 4-amino compound using elemental bromine and an alkali metal hydroxide, which is converted into a highly active compound using the corresponding chlorobenzene derivative in the presence of lithium hydroxide and dimethylsulfoxide, for example, 2,2-difluoro-4- (2,4-dinitro-6-
Trifluoromethylanilino) -benzo [1,3] dioxole and some anilino- having biocidal activity
It is already known that benzo [1,3] dioxoles can be obtained (see EP 198,797).

[0003]

DISCLOSURE OF THE INVENTION General formula (I)

[0004]

[Chemical 5]

In the formula, R represents fluorine, chlorine, bromine or nitro; Hal represents chlorine or fluorine, and is a novel 2,2-dihalogeno-benzo [1,3] substituted at the 4-position. Dioxoles were found.

The compounds are, in particular, the following compounds:

[0007]

[Chemical 6]

Further, when Hal represents chlorine: a) General formula (II)

[0009]

[Chemical 7]

In the formula, R represents fluorine, chlorine, bromine or nitro.
3) dioxols with the corresponding chlorinating agent, if appropriate in the presence of a free radical initiator or high-energy light, and if appropriate in the presence of a solvent, at a temperature between 0 ° C and 200 ° C. When the compounds represented by the formulas (Ia) to (Id) are reacted, or when Hal represents fluorine, b) 2,2-substituted 4-positions represented by the formulas (Ia) to (Id) The dichloro derivative, if appropriate in the presence of a solvent, is reacted with hydrogen fluoride at a temperature between −20 ° C. and + 80 ° C. to give compounds of the formulas (Ic) to (Ih), the general formula (I)

[0011]

[Chemical 8]

Where R is as defined above and Ha
It has been found that 4-disubstituted 2,2-dihalogenobenzo [1,3] dioxoles can be obtained, wherein 1 represents chlorine or fluorine.

The 2,2-dihalogeno-benzo [1,3] dioxole of the present invention, which is substituted at the 4-position, is defined by formula (I) or formulas (Ia) to (Ih).

If in method a) the starting material 4-
Using fluorobenzo [1,3] -dioxole and phosphorus pentachloride, the reaction pathway can be represented by the following reaction scheme:

[0015]

[Chemical 9]

If in method b) the starting material is 2,
Using 2-dichloro-4-fluoro-benzo [1,3] dioxole and hydrogen fluoride, the reaction pathway can be represented by the following reaction scheme:

[0017]

[Chemical 10]

Benzo [1,3] dioxole represented by the formula (II) and substituted at the 4-position with chlorine or nitro, which is necessary as a starting material in the method a) of the present invention, is known (EP 82 681, EP 82 681). DE 3 742 515 and
J. Heterocycl. Chem. 28 (1991) 625).

The process a) of the chlorination reaction can be carried out with all customary chlorinating agents. These include, for example, phosphorus pentachloride, phosphorus trichloride and chlorine, elemental chlorine and also sulfuryl chloride.

Phosphorus pentachloride is preferably used.

If elemental chlorine or sulfuryl chloride is used, the reaction is preferably carried out in the presence of a free radical initiator or in the presence of UV light.

The free radical initiator is used in an amount of 0.0001 to 0.05 mol per mol of the compound of formula (II).

Free radical initiators which can be used are, for example, AiBN, dibenzoyl peroxide, succinyl peroxide, di-t-butyl peroxide and diacetyl peroxide. Method a) can be carried out in the presence of a solvent. Possible solvents are chlorinated hydrocarbons such as carbon tetrachloride, methylene chloride and the like.

If phosphorus pentachloride and phosphorus trichloride / chlorine are used, the reaction is preferably carried out without solvent, while if chlorine or sulfuryl chloride is used, preferably carried out in a solvent such as carbon tetrachloride. Preferably.

The ratio of chlorinating agent to the compound of formula (II) can be varied within a considerable range and is from 2: 1 to 4: 1, preferably 2.2: 1.

The temperature in method a) can be varied within a considerable range. The reaction is generally performed at 0 ° C to 200 ° C.

If elemental chlorine or sulfuryl chloride is used as the chlorinating agent together with the free radical initiator, the reaction is preferably carried out at 60 ° C-100 ° C.

When using elemental chlorine or sulfuryl chloride with UV initiators, it is preferred to carry out the reaction at 10 ° C to 40 ° C.

In the case of phosphorus pentachloride or phosphorus trichloride and chlorine, the reaction is carried out between 80 ° C. and 180 ° C., in particular 90 ° C. and 160 ° C.
It is preferred to carry out between 0 ° C.

The reaction time can also be varied. The reaction is carried out until the evolution of hydrogen chloride has ceased and the mixture is worked up in a conventional manner, for example by distilling off the solvent if appropriate and fractionating under vacuum.

In process b), as starting materials, the dichloro compounds obtained in process a) and defined by formula (I) or formulas (Ia) to (Id), which are novel and form part of the invention. To use.

To carry out the method b), hydrogen fluoride is used to replace the chlorine atom at the 2-position with a fluorine atom.

If appropriate, method b) can be carried out in a solvent. Suitable solvents are alkylated or chlorinated aromatics, preferably toluene or chlorobenzene.

When toluene is used as the solvent, the weight ratio of hydrogen fluoride to toluene varies between 1: 2 and 2: 1 and is preferably 1: 1.

The ratio of hydrogen fluoride to dichloro compound used varies between 2: 1 and 20: 1, preferably 10: 1.

The temperature in method b) can be varied within a considerable range. Generally the reaction is between -20 ° C and + 80 ° C, preferably between -10 ° C and 60 ° C and particularly preferably -1.
It is carried out at temperatures between 0 ° C and 30 ° C.

The reaction time also varies; the reaction is carried out until the evolution of hydrogen chloride has ended. Work-up is carried out in the customary manner, for example by distilling off excess hydrogen fluoride and then distilling; or phase-separating, if appropriate after washing the organic phase with water, drying or by adding alkali metal fluorides. The organic phase is distilled;

The compounds of formula (I) are valuable starting materials for the preparation of highly active biocides. A nitro compound can be reduced to an amino compound, which is reacted with a chlorobenzene derivative to obtain the highly active compound 2,2-difluoro-4.
It is possible to obtain-(2,4-dinitro-6-trifluoromethyl-anilino) -benzo [1,3] dioxole, which protects against pests, preferably plant infectious fungi or bacteria, and also insects and mites. It is used as a drug for extermination (see EP 198 797).

[0039]

[Chemical 11]

This known compound of the formula (A) has a very advantageous spectrum of biocidal action, which is
It meets the requirements for use against the representatives of bacteria, insects and mites, especially against phytopathogenic fungi and bacteria. It has very good therapeutic, systemic and especially prophylactic properties and can be used to protect a large number of cereal plants. By using the active compound of formula (A), it is possible to suppress or destroy pests generated on plants or plant parts (fruits, flowers, leaves, stems, bulbs, roots) of various cereal plants. The resulting plant parts that continue to grow further remain protected from phytopathogenic microorganisms and insects.
The order Aclarina can be eliminated even more successfully with the active compounds of the formula I.

As microbicides, active compounds of the formula (A) are active against phytopathogenic fungi, for example belonging to the following classes: Fungi imperfecti
(For example, Botrytis, Helminthosporium, Fusarium,
Septoria, Cercospora
And Alternaria; Basidiom
ycetes) (for example the genus of Hemileia, Thizocotonia and Puccinia);
And oomycetes (Oomycete) belonging to the genus Phycomycetes
s) (eg Plasmopara viticola); especially Ascomycetes (eg Ventuia).
ria), Podospharea, Erysiphe, Monilinia and Uncinula), and the compounds of formula (A) are systemically effective. Furthermore, it can be used as a dressing agent for the treatment of seeds (fruits, bulbs, cereals) and seedlings and provides protection against fungal infections and phytopathogenic fungi occurring in the soil.

As insecticides, the compounds of formula (A) are of the following order: Lepidoptera, Coleoptera (C).
oleoptera, Homoptera, Heteroptera, Diptera, Diptera, Thysanoptera, Orthoptera, Blattaria, Anoplura, Siphonaptera, Malopha
a), Thysanura, Isopter
It can also be used for combating insects of a), Psocoptera, and Hymenoptera.

Further, the compound of formula (A) is a mite (the orde).
r of Acarina), such as Ioxididae, Argasidae, Tetranychidae, and Dermanishidae.
nyssidae) is suitable for exterminating the family. The compounds of formula (A) are phytopathogenic mites such as Tetranitidae and Phytoptipalpidae [spider mites], Tarsonemidae.
idae) [tarsonemids] and Eriophydiae [gall mites] can be used successfully.

The nitro compounds of the formula (I) or formula (Ih) according to the invention can be used directly as precursors, for example for the synthesis of compounds of the formula (A). The advantage is that the 2,2-difluoro derivative is obtained in the same way in two identical reaction steps starting from the known compound without side reactions and is free of environmentally hazardous metal fluorides as in the known method. .. Furthermore, the method is a four-step reaction, and since the method also involves the reduction of a nitro group to an amino group, it has only three steps.

The 4-bromo-2,2-difluorobenzo (1,3) dioxole of the present invention is, for example, 3- (2,2-
Difluorobenzo [1,3] -dioxolo-4-yl)
It can be used as a starting material for the synthesis of -4-cyanoprilol. This compound, a process for its preparation and its use in microbicides is described in EP 206 999. This compound is prepared from the corresponding cinnamic acid nitrile and tosmic, and the cinnamic acid nitrile is reacted via the diazonium salt from the corresponding amine to give the 1-chloro-1-cyanoethyl derivative, which converts the cinnamic acid nitrile. give.

[0046]

[Chemical 12]

The cinnamic acid nitrile is reacted with acrylonitrile in the presence of palladium acetate in a one-step reaction with 4-bromo- of the present invention.
It can be easily synthesized from 2,2-difluorobenzo (1,3) dioxole in an excellent yield (97% of theory) (see the production section). The reaction giving the final product is carried out as described above.

Several steps in the reaction have been omitted and the palladium acetate used can be recovered, so that the wastewater is free of pollution, eg when copper chloride is used in the second step of the known process. ..

Generally speaking, the novel products are starting materials for the synthesis of the most diverse and highly active compounds in the plant protection or pharmaceutical field. There should always be a demand for new precursors that are easy to manufacture, so they should be regarded as an advance.

[0050]

EXAMPLES Manufacturing Examples Example 1

[0051]

[Chemical 13]

54 g (0.2 mol) of 4-bromo-2,2
Dichloro-benzo [1,3] dioxole together with 50 g of anhydrous hydrogen fluoride in 75 ml toluene at 0 ° C.
Stir vigorously for hours. Then pour the reaction mixture onto ice,
Neutralize with excess potassium hydroxide, extract with ether, wash the extract with 5% strength sodium bicarbonate solution and water, dry over magnesium sulfate, concentrate and distill the product.
33.6 g of 4-bromo-2,2-difluoro-benzo [1,3] dioxole having a boiling point of 67 ° C./16 mbar
(71% of theory) is obtained.

Example 2

[0054]

[Chemical 14]

108 g (91% purity, 416 mmol)
4-Nitro-2,2-dichlorobenzo [1,3] dioxole, 100 ml of toluene and 100 g of anhydrous hydrogen fluoride are stirred vigorously at 0 ° C. until most of the starting material has reacted by GC *.

Most of the hydrogen fluoride was distilled off under vacuum,
The residue is poured onto ice, the mixture is neutralized with excess potassium hydroxide and extracted with ether. The extract is washed with 5% strength sodium bicarbonate solution, dried over magnesium sulphate, concentrated and the product distilled under vacuum. Boiling point 120-122 ° C /
32 g of 16 mbar 4-nitro-2,2-difluoro-benzo [1,3] dioxole (38% of theory)
Is isolated.

* (Gas chromatography) Example 3

[0058]

[Chemical 15]

1512.8 g (0.75 mmol) of 4-bromo-benzo [1,3] dioxole 312.8 g (1.
(5 mmol) phosphorus pentachloride are added portionwise under a stream of dry nitrogen with exclusion of moisture and the mixture is heated at 120 ° C. for 3 hours. The phosphorus trichloride is distilled off and the product is distilled under vacuum.
Boiling point 126-129 ° C / 20 mbar and melting point 49-
4-bromo-2,2-dichlorobenzo [1,3] at 51 ° C
198 g (98% of theory) of dioxoles are obtained.

Example 4

[0061]

[Chemical 16]

77.4 g (467 mmol) of 4-nitro-benzo [1,3] dioxole 97.4 g (467)
(Mmol) phosphorus pentachloride and the mixture is heated under nitrogen until it liquefies. And 97.4g (46
(7 mmol) phosphorus pentachloride and the mixture is heated at about 140 ° C. until the evolution of HCl gas ceases. Then, the formed phosphorus trichloride is distilled off.

After distillation under high vacuum, boiling point 120-12
108 g of 4-nitro-2,2-dichloro-benzo [1,3] dioxole at 1 DEG C./0.6 mbar (9 theoretical)
8%) is obtained.

The following compounds can be prepared in an analogous manner to the above Preparation Examples:

[0065]

[Chemical 17]

[0066]

[Further processing stage]

[0067]

[Chemical 18]

9.5 g (0.04 mol) of 4-bromo-
2,2-Difluoro-benzo [1,3] dioxole and 3.2 g (0.06 mol) of acrylonitrile were initially added to 10
Charge to 0 ml dimethylformamide, and add 0.1
8 g (0.82 mmol) of palladium acetate, 8.4 g
(0.10 mol) sodium bicarbonate and 4.5 g (0.01
6 mol) of tetrabutylammonium chloride are added and the mixture is heated at 120 ° C. After reacting for 16 hours, a further 1.6 g (0.03 mol) of acrylonitrile, 0.0
9 g (0.41 mmol) of palladium acetate, 4.2 g
(0.05 mol) sodium bicarbonate and 2.25 g (0.0 mol)
(08 mol) tetrabutylammonium chloride are added to the reaction mixture to complete the reaction and again the mixture is heated at 120 ° C. for 16 hours. Pour it into water,
Extract with ethyl acetate, wash the extract with water and 2N hydrochloric acid, dry and remove the solvent under vacuum.

8.2 g (97% of theory) of 2,3-difluoromethylenedioxycinnamic acid nitrile are obtained as a brown oil.

Further processing is carried out as described in the literature.

Thus, the main features and embodiments of the present invention are summarized as follows. 1. General formula

[0072]

[Chemical 19]

In the formula, R represents fluorine, chlorine, bromine or nitro, and Hal represents chlorine or fluorine. 2,2-dihalogenobenzo [1,3] substituted at the 4-position
Dioxoles.

2. Formula (I) according to claim 1, wherein R represents fluorine, chlorine, bromine or nitro, and Hal represents fluorine.
Compound of.

3. A compound of formula (I) according to claim 1 in which R represents fluorine, chlorine, bromine or nitro and Hal represents chlorine.

4. R represents bromine or nitro, Hal
A compound of formula (I) according to claim 1 in which is chlorine.

5. R represents bromine or nitro, Hal
A compound of formula (I) according to claim 1 in which is fluorine.

6. When Hal represents chlorine: a) General formula (II)

[0079]

[Chemical 20]

In the formula, R represents fluorine, chlorine, bromine or nitro, and benzo [1,
3] dioxols are chlorinated, if appropriate in the presence of a solvent; or if Hal represents fluorine: b) the following formulas (Ia) to (Id)

[0081]

[Chemical 21]

Wherein R is as defined above and is obtained in a) substituted at the 4-position as shown in
A dichloro compound is reacted with hydrogen fluoride, if appropriate in the presence of a solvent;

[0083]

[Chemical formula 22]

Wherein R is as defined above and Ha
l represents chlorine or fluorine, and is a process for producing 2,2-dihalogenobenzo [1,3] dioxole substituted at the 4-position, represented by:

7. Use of compounds of formula (I) for the preparation of highly active substances in various fields.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Albrecht Malholt Germany Day 5090 Lef Erkusen 1 Karl-Dowisberg-Schutlerse 329

Claims (3)

[Claims] 1. A general formula: In the formula, R represents fluorine, chlorine, bromine or nitro, and H
al represents chlorine or fluorine, and is 2,2-dihalogenobenzo [1,3] dioxole substituted at the 4-position represented by: 2. When Hal represents chlorine: a) General formula (II): Where R represents fluorine, chlorine, bromine or nitro, chlorinated benzo [1,3] dioxole substituted at the 4-position, if appropriate in the presence of a solvent; or Hal is fluorine. In the case of representing a prime, b) the formulas (Ia) to (Id) Wherein R is as defined above, and the 2,2-dichloro compound obtained in a) substituted at the 4-position is reacted with hydrogen fluoride, if appropriate in the presence of a solvent; A general formula (I) characterized by: In the formula, R is as defined above and Hal represents chlorine or fluorine.
Process for producing dihalogenobenzo [1,3] dioxoles. 3. Use of a compound of formula (I) for the preparation of highly active substances in various fields.